Preparation of an active intermediate

ABSTRACT

A process for the preparation of an organic reactive intermediate that contains a combination of epoxy groups, hydroxy groups and unsaturated groups wherein the process can be utilized to control the amounts of each of the functional groups in the final product. The reactive intermediates are prepared from natural triglyceride plant and animal oils containing unsaturation.

This application claims priority from U.S. Provisional Application Ser.No. 61/341,926, filed Apr. 7, 2010.

BACKGROUND OF THE INVENTION

The contacting of a plant oil, carboxylic acid and hydrogen peroxide iswell documented and can easily be found in the public domain. The focusof prior work in this area has been the preparation of epoxides andpolyols from unsaturated triglycerides found commonly in a wide range ofoil seeds.

These epoxides and polyols are polymerized with isocyanates to formpolyurethanes, the isocyanate reacting with active epoxide and hydroxylsites. The manufacture of these products using the materials outlinedabove requires heat, agitation, and owing to solubility limitations ofthe components, involves more than one liquid phase.

The desired end product of the resulting polyol is one that has activeprimary and secondary hydroxyl sites, with no interfering or competingfunctional groups. The desired end product of the resulting epoxide is aproduct that has no active, interfering or competing primary orsecondary hydroxy sites. There has been very little work done on thepreparation and use of hybrids comprised of active epoxide and hydroxylsites in the same molecule and end use applications of the same.

This technology extends to the use of all mono and poly-unsaturatedplant and animal derived triglycerides including those that haveundergone transesterification to form esters, in what is commonly knownas the biodiesel process.

Camelina sativa is a cruciferous oilseed plant. Also known as false flaxor gold of pleasure, this natural oil source has been in use sinceBronze and Iron Ages. The seeds contain 30-40% oil on a dry basis. Theoil finds use in cooking and high omega-3 preparations such as saladdressing, mayonnaise, ice cream, pet foods, and, biodiesel. It has afatty acid profile of 10% of saturated, 34% mono-unsaturated and 56%poly-unsaturated, with alpha-linolenic acid accounting for 35% of theoil.

The unsaturated fatty acid sites in camelina oil and all triglyceridesare composed of carbon-carbon double bonds. These alkene sites are ofparticular interest in the preparation of functionalized plant oils forindustrial use. This oil fits very well into the instant invention, inthat, the oils that are preferred are those oils, or combination of oilsthat have up to C₂₂ carbon atoms.

These reactive alkene sites offer an opportunity to transform thecamelina and other plant or animal derived oils into value addedproducts suitable for use in the polyurethane, healthcare, energy, andother industries.

This invention is directed to a process for transforming these oils intoreactive intermediates that contain moieties with a combination ofalkenes, and either hydroxyl or epoxide, or a combination of hydroxyland epoxide, reactive sites in the same product.

THE INVENTION

Thus, what is disclosed and claimed herein is a process for thepreparation of organic reactive intermediates that contain a combinationof epoxy groups, hydroxy groups and unsaturated alkene groups whereinthe process can be utilized to control the amounts of each of thefunctional groups in the final product.

In one embodiment, the process comprises a multi-step preparationconsisting of a first step of predetermining the concentrations ofhydrogen peroxide and organic acid to be used in the process wherein the“organic acid” means that it is selected from group consisting of aceticacid, peracetic acid, formic acid, and performic acid.

Thereafter, predetermined amounts of plant and/or animal oils in anyform, such as crude, refined, refined and deodorized, or, refined,bleached and deodorized (RBD), or a combination thereof consisting ofplant oils and another consisting of plant oils and animal oils, havingat least 1% by weight of unsaturation, based on the weight of the oils,or combinations thereof, is combined with the predetermined amounts oforganic acid and hydrogen peroxide, in a reaction vessel. It iscontemplated within the scope of this invention to use a mineral acidsuch as sulfuric acid during this step, as a catalyst.

The mixture is then heated to at least 45° C. under an inert atmospherefor a period of time of thirty (30) minutes to 168 hours, with stirring.

Thereafter, concentrating and deodorizing the product by sparging usinga material selected from the group consisting of nitrogen, steam andair, at a temperature of 90° C. to 130° C. to provide a product havingan acid number of 2.5 to 10 mg KOH/g and a hydroxyl number of up toabout 230.

In a second embodiment, the process comprises a multi-step preparationconsisting of a first step of predetermining the concentrations ofhydrogen peroxide and organic acid to be used in the process.

Thereafter, a predetermined amount of fatty acid chains cleaved fromanimal and plant triglyceride backbone, or the methyl esters derivedfrom the same, that are by-products of the manufacture of biodiesel asstarting materials, are added. All grades of unsaturated biodiesel(methyl or ethyl esters) serve as suitable starting raw material forthis process. These materials must also have at least 1% by weight ofunsaturation, based on the weight of the biodiesel raw material. Thesematerials are combined with the predetermined amounts of organic acidand hydrogen peroxide, in a reaction vessel. As set forth above, amineral acid such as sulfuric acid can be used as a catalyst during thisstep.

The mixture is then heated to at least 45° C. under an inert atmospherefor a period of time of thirty (30) minutes to 168 hours, with stirring.

Finally, the product is concentrated and deodorized by sparging using amaterial selected from the group consisting of nitrogen, steam and airat a temperature of 90° C. to 130° C. to provide a product having anacid number of up to 10 mg KOH/g.

The process is designed to give triglyceride hybrids having alkene,epoxide and hydroxyl content at variable levels. These products arefunctionally different from prior art materials in structure andchemical reactions when employed in industrial applications due to thereaction characteristics of the functional groups present.

This process provides intermediates having high hydroxyl numbers (up to230) with low color such as Gardner Color number of seven (7) or lesswith the preferred level being at a Gardner Color number of five (5) orless and a most preferred product having a Gardner Color number of three(3) or less.

This process also provides intermediates having high acid number that isan acid number of 2.5 to 10 mg KOH/g.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph that can be used to determine the concentrations andratios of the various components for the reaction using 25% or 70% w/whydrogen peroxide.

DETAILED DESCRIPTION OF THE INVENTION

The invention described and disclosed herein deals with a process forthe preparation of organic reactive intermediates that contain acombination of unsaturated groups, and epoxy groups or hydroxy groups,or a combination of epoxy groups and hydroxy groups. The organicreactive intermediates are derived from natural triglyceride plantand/or animal oils or combinations having at least one percent (1%) byweight of unsaturation, based on the weight of the natural triglycerideoils.

Table I is a table listing many of the oils that can be used althoughthis invention is not limited by such disclosure.

TABLE I Triglycerides and their Iodine Values Oil Iodine Value Muttontallow 40 Beef tallow 50 Palm oil 54 Olive oil 81 Castor oil 85 Peanutoil 93 Rapeseed oil 98 Cotton seed oil 105 Sunflower oil 125 Soybean oil130 Tung oil 168 Linseed oil 190 Camelina oil 150 Sardine oil 185

Preferred are plant oils, camelina, canola, jatropha, soy, and animaloils, sardine, herring, and beef tallow.

Especially preferred are linseed, canola, soy, jatropha, camelina andsardine oils. Camelina oil has an approximate iodine number of about 150as opposed to soy oil at about 130. Iodine number is a reflection of thelevel of unsaturation (carbon-carbon double bonds) present in atriglyceride. Approximately 90% of the camelina triglyceride isunsaturated. The plant and animal oils useful herein can be crude,refined, refined and deodorized or, refined, bleached and deodorized(RBD) types of plant and animal oils.

Triglycerides can also be selected from non-food sources and preferablythose with natural levels of alkenes, epoxides, alcohols and carboxylicacids, or any combinations of these, or other functional groups.

Of further interest in this invention are those oilseeds that have beengenetically modified to enhance the seed's epoxide and/or hydroxycontent. Further, of interest are those oil seeds that meet the abovecriteria but are considered low input industrial oil seed crops that donot compete with food crops. Preferred examples of these materials arevernonia anthelmintica seed oil, chrysanthemum coronarium seed oil,camelina sativa seed oil, and ricinus communis seed oil.

For purposes of this invention, the natural oils and esters must have atleast one percent (1%) of unsaturation. The oils are combined with apredetermined amount of hydrogen peroxide and organic acid whichconverts a portion of the unsaturated carbon-carbon double bonds intoepoxy groups, and then a portion of the epoxy groups into hydroxygroups.

The amount of conversion of the above-mentioned functional groups isdependent on the amounts and ratios of the hydrogen peroxide and acid,and on the time and temperature of reaction.

With reference to FIG. 1, there is shown a graph that can be used todetermine the concentrations and ratios of the various components forthe reaction in order to end up with a product having the approximateamounts of functional groups that are desired.

For example,

From FIG. 1: Triglyceride (Camelina Oil) reaction profile

Example 1

If the desired product requires a hydroxyl number of 115 and epoxidecontent of 2.4%, the following raw materials are required.

Hydrogen Peroxide (50% w/w): 287 g

1. Acetic Acid, glacial: 253 g

2. Camelina oil (Refined), Iodine number 150: 1045 g

3. Reaction time: 8 Hrs

Example 2

If the desired product requires a hydroxyl number of 167 and epoxidecontent of 0.5%, the following raw materials are required.

1. Hydrogen Peroxide (70% w/w): 205 g

2. Acetic Acid, glacial: 253 g

3. Camelina oil (Refined), Iodine number 150: 1045 g

4. Reaction time: 13 hrs

Example 3

If the desired product requires a hydroxyl number of 44 and epoxidecontent of 4.0%, the following raw materials are required.

1. Hydrogen Peroxide (25% w/w): 487 g

2. Acetic Acid, glacial: 215 g

3. Camelina oil (Refined), Iodine number 150: 888 g

4. Reaction time: 21 hrs

The preferred order of addition is oil, followed by the simultaneousaddition of acid and hydrogen peroxide. A second option is oil followedby acid and finally hydrogen peroxide. The preferred option is thesimultaneous addition of oil, acid and hydrogen peroxide. In the firsttwo cases the acid and oxidant are metered in. In the preferred option,the oil, acid and hydrogen peroxide are all metered in.

The concentration and deodorization steps are the same as describedearlier for all three (3) examples given.

The reaction of the unsaturated functional plant and animal oils to aportion of epoxy groups and a portion of hydroxy groups is enhanced bythe use of acetic or formic acid containing water and these componentsare put into the reaction at the very beginning of the process. Theformic acid, if substituted for acetic acid, speeds up the epoxide ringformation and also accelerates the epoxide ring opening to form hydroxygroups. Alternately, a mineral acid such as sulfuric acid can be used asa catalyst to accelerate the reaction.

It has been determined that this reaction can be carried out at or nearatmospheric pressure. Also, it is contemplated within the scope of thisinvention to carry out this reaction under an inert blanket of gas, suchas nitrogen, helium, argon or the like.

The reaction vessel must have stirring capabilities and must have theability to handle subsurface inert gases during the reaction sequence,and must have heating and cooling capabilities. Further, adequateventing capabilities must be built into the system to handle systemupset from the possible decomposition of hydrogen peroxide.

The mixture is stirred and heated for at least thirty (30) minutes andmust be heated to at least 45° C., with or without the use of an inertgas cover, for the duration of the reaction time.

It has been found that some of the beneficial properties of theintermediates, such as high hydroxyl number and controlled epoxidecontent, come from this part of the reaction sequence wherein, thematerials are heated for thirty (30) minutes to one hundred sixty eight(168) hours, with stirring.

Refining the product means concentration and deodorization of theproduct using vacuum and sparging using a material selected fromnitrogen, steam, and air at a temperature of from 90° C. to 130° C. toprovide a product. It is preferred to keep the temperature closer to 90°C. in order to avert the appearance of color. The concentration anddeodorization step results in lower levels of decomposition productssuch as aldehydes and ketones which are present in other preparationprocesses. It has been found that beneficial properties of theintermediates, such as low odor, low color, low water content come fromthis part of the concentration and deodorization step.

It should be noted by those skilled in the art that this product doesnot have to be neutralized at any point during or after the reaction.

The preferred range for acid in this invention is 80 to 100 percent andthe preferred range for the hydrogen peroxide is from 25 to 85 percenton a weight by weight basis, it being understood that peracetic andperformic acids can also be used. Peracetic or performic acids aremixtures of hydrogen peroxide and acetic acid and formic acidrespectively, in aqueous solutions. Peracetic acid is a transparent,faint blue colored liquid that has a piercing odor and a pH of about2.8.

The epoxide range for the final product is in the range of 0.0 to 4.1w/w percent and the hydroxyl number up to about 230. Preferred for thisinvention is an epoxide content of 0.1 to 3.5 w/w percent. Morepreferred are epoxide ranges from 1.2 to 3.0 percent.

Further, it is understood that this process contemplates using the fattyacid chains cleaved from the animal and plant triglyceride backbone orthe methyl esters derived from the same as starting materials. In short,all grades of unsaturated biodiesel (methyl or ethyl esters) serve assuitable starting raw material for this process and are considered to bewithin this scope of this invention.

1. A process for the preparation of organic reactive intermediates thatcontain unsaturated moieties and moieties selected from the groupconsisting of: i hydroxyl groups, ii epoxide groups, and, iii hydroxyland epoxide groups, said process comprising: A. predetermining theconcentrations of aqueous hydrogen peroxide and organic acid to be usedin the process, said acid selected from the group consisting of: i.acetic acid, ii. peracetic acid, iii. formic acid, and, iv. performicacid; B. combining a predetermined amount of oil selected from the groupconsisting of: a. natural triglyceride plant oils, and, b. animal oils,and, c. a combination of natural triglyceride oils and animal oils, eacha. b. and c. having at least 1% by weight of unsaturation selected fromthe group consisting of: i mono-unsaturation, ii poly-unsaturation, and,iii combinations of mono and poly unsaturation, based on the weight ofthe oils, with the predetermined amounts of organic acid and hydrogenperoxide in a reaction vessel to form a mixture; C. heating the mixtureto at least 45° C. under an inert atmosphere for a period of time offrom thirty minutes to 168 hours, with stirring; D. concentrating anddeodorizing the product from C. by sparging using a material selectedfrom the group consisting of i. nitrogen, ii. steam, and, iii. air, at atemperature of 90° to 130° C. to provide a product having an acid numberof 2.5 to 10 mg KOH/g.
 2. A process as claimed in claim 1 wherein instep D., there is a vacuum applied.
 3. A process as claimed in claim 2wherein the vacuum is in the range of 5 inches of mercury to 29.5 inchesof mercury.
 4. A process as claimed in claim 1 wherein step D., there isno vacuum applied.
 5. A process as claimed in claim 1 wherein theintermediate has an epoxide content of 0.0 to 4.1 weight percent.
 6. Aprocess as claimed in claim 1 wherein the intermediate has an epoxidecontent of 0.1 to 3.5 weight percent.
 7. A process as claimed in claim 1wherein the intermediate has an epoxide content of 0.8 to 3.0 weightpercent.
 8. A process as claimed in claim 1 wherein the intermediate hasan epoxide content of 1.2 to 2.8 weight percent.
 9. A process as claimedin claim 1 wherein in step D. wherein the steam has a pressure of 10 to50 psig.
 10. A process as claimed in claim 9 wherein the steam has apressure of 20 to 40 psig.
 11. A process as claimed in claim 9 whereinthe steam has a pressure of 25 to 35 psig.
 12. The process as claimed inclaim 1, wherein, in addition, there is a mineral acid present.
 13. Theprocess as claimed in claim 12 wherein the mineral acid is sulfuricacid.
 14. The process as claimed in claim 1, wherein, the molar ratio ofhydrogen peroxide to oil is from about 1/1 to 8/1.
 15. The process asclaimed in claim 1 wherein the molar ratio of acid to oil is from about1/1 to 5/1.
 16. A product prepared by the process of claim 1 wherein theintermediate has 0.1 weight percent water or less, an acid number of 2.5to 10 mg KOH/g and a hydroxyl number of up to about
 230. 17. The processof claim 1 wherein the hydrogen peroxide is in the range of 25 to 85percent w/w and the organic acid is in the range of 80 to 100 percentw/w.
 18. The process of claim 1 wherein the acid is acetic acid.
 19. Theprocess of claim 1 wherein the acid is formic acid.
 20. A process asclaimed in claim 1 wherein the in intermediate has a hydroxyl number ofup to about
 230. 21. The process of claim 1 wherein the addition of oilis followed by the simultaneous addition of acid and hydrogen peroxide.22. The process of claim 1 wherein the addition of oil is followed byacid and then hydrogen peroxide.
 23. The process of claim 1 wherein theintermediate has a biobased content of about 80 to 90 weight percent.24. The process of claim 1 wherein the intermediate has a biobasedcontent of more than 90 percent by weight.
 25. A process for thepreparation of organic reactive intermediates that contain unsaturatedmoieties and moieties selected from the group consisting of: i hydroxylgroups, ii epoxide groups, and, iii hydroxyl and epoxide groups, saidprocess comprising: A. predetermining the concentrations of aqueoushydrogen peroxide and organic acid to be used in the process saidorganic acid being selected the group consisting of i. acetic acid, and,ii. formic acid; B. combining a predetermined amount of materialsselected from the group consisting of i fatty acid chains cleaved fromanimal triglyceride backbone, ii plant triglyceride backbone, iii methylesters derived from fatty acid chains cleaved from animal triglyceridebackbone, and, iv methyl esters derived from fatty acid chains cleavedfrom plant triglyceride backbone, that are by-products of themanufacture of biodiesel, each of i to iv having at least 1 percent ofunsaturation selected from the group consisting of: i mono-unsaturation,ii poly-unsaturation, and, iii combinations of mono and polyunsaturation, based on the weight of the oils, with the predeterminedamounts of organic acid and hydrogen peroxide in a reaction vessel toform a mixture; C. heating the mixture to at least 45° C. under an inertatmosphere for a period of time of from thirty minutes to 168 hours,with stirring; D. concentrating and deodorizing the product from C. bysparging using a material selected from the group consisting of i.nitrogen, ii. steam, and, iii. air, at a temperature of 90° to 130° C.to provide a product having an acid number up to about 10 mg KOH/g. 26.A product prepared by the process of claim 25 wherein the intermediatehas 0.1 weight percent water or less, an acid number of 2.5 to 10 mgKOH/g and a hydroxyl number of up to about
 230. 27. The product of claim1 wherein the product has a Gardner Color number of 7 or less.
 28. Theproduct of claim 26 wherein the product has a Gardner Color number of 7or less.
 29. The product of claim 1 wherein the product has an inherentodor score of 7 or higher on the General Motors GME 60276 odor testingprocedure.
 30. The product of claim 25 wherein the product has aninherent odor score of 7 or higher on the General Motors GME 60276 odortesting procedure.